Thermoplastic polyurethane elastomers



United States Patent 3,503,927 THERMOPLASTIC POLYURETHANE ELASTOMERS Eugene Yue Chieh Chang and Samuel Kaizerman, Bridgewater Township, Somerset County, N.J., assignors to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed June 7, 1968, Ser. No. 735,201 Int. Cl. C08g 22/04, 22/08 US. Cl. 260-47 6 Claims ABSTRACT OF THE DISCLOSURE An improved thermoplastic polyurethane elastomer containing a cross-linked network structure wherein the cross-linking is labile to heat. The cross-linking is provided by reaction between a diol having a phenolic substituent and isocyanate groups present in the polyurethane prepolymer.

This invention relates to novel thermoplastic, polyurethane elastomers. More particularly, it relates to a method of making thermoplastic, polyurethane elastomers containing a cross-linked network structure wherein the cross-linking is labile to heat. It relates further to the curing of polyurethane prepolymers using a diol having a phenolic substituent as the curing agent.

Polyurethane elastomers have been known for a considerable number of years. Thermoplastic polyurethane elastomers in particular have been of more recent interest. Such elastomers are desirable because of an unusually good combination of mechanical properties, and adaptability to a wide range of use requirements.

Thermoplastic polyurethane elastomers are generally based on the formation of a prepolymer. As employed in the polyurethane art, and in this specification as well, the term prepolymer is intended to mean a low molecular weight (generally below 5000) reaction product of a molar excess of an organic diisocyanate compound with either (1) a hydroxy-terminated polyester or (2) a hydroxy-terminated polyether or (3) a combination of (l) and (2). The prepolymers are isocyanate-terminated as a result of the use of the above-mentioned molar excess of diisocyanate, and are usually viscous liquids or low-melting, wax-like solids.

Thermoplastic elastomers have been heretofore obtained when such a prepolymer was cured or chainextended to a high molecular weight polymer with a stoichiometric quantity of a difunctional organic copound reactive with the terminal isocyanate groups. The compounds most commonly used as curatives in the preparation of thermoplastic polyurethane elastomers were diols such as for example 1,4-butanediol, 1,6-hexane-diol or hydroquinone bis(hydroxyethyl)ether, commonly referred to as PEHQ. Thermoplasticity was correlated to a lack of substantial cross-linking in the polymer. Thus, these thermoplastic polyurethanes are normally substantially linear, relatively low melting structures. They are capable of repeated extrusion, injection or compressionmolding and milling without excessive thermal breakdown, decomposition or loss of mechanical properties. They can be processed, with perhaps slight modifications, by the Well-known techniques used for other thermoplastic materials such as polystyrene, polyethylene, polypropylene, etc.

One of the problems inherent in the conventional linear thermoplastic polyurethane elastomers is the relatively slow recovery of elastomeric properties following mechanical and thermal treatment (milling, extrusion, etc.), probably as a result, mainly, of the slow realignment (due to chain entanglements, etc.) of polymer chains to reform the strong secondary or Van der Waals forces which are "ice the major contributor to the good mechanical properties of linear polyurethane elastomers. Another deterrent to the acceptance of these polymers is the high degree of set which results when the polymer is subjected to stress (i.e., either from stretching or compressive force). This is a phenomenon related to the recovery of the polymer as discussed above. Set, for example, sometimes is found to be as high as Recovery from this deformation is usually slow under normal temperature conditions and constitutes a severe limitation to the use of the elastomer. A detailed discussion of the forces at work in the determination of properties as related to structural features in the polymer is beyond the scope of this specification, but an excellent review of this relationship can be found in Saunders and Frisch, Polyurethanes: Chemistry and Technology, Part I, pages 261-346 (Interscience Publishers, 1962).

Speedy recovery of mechanical properties (e.g. improved set characteristics) can be aided by the incorporation into the normally linear polymer structure of a small degree of cross-linking. This is a well-known structureproperty relationship. However, conventional crosslinking is a structural feature that is inconsistent with thermoplasticity. Polymers containning a cross-linked structure are normally considered thermosetting. Attempts to incorporate primary chemical cross-links into a thermoplastic polyurethane elastomer via the formation of some degree of allophanate linkages as a result of using less than a stoichiometric quantity of curative, have been made. The resulting polymer has relatively limited processability. What is needed, therefore, is a means of obtaining polyurethane elastomers which are thermoplastic and yet characterized by good recovery of mechanical properties after thermal treatment.

It is accordingly an object of this invention to provide a means for obtaining a processable thermoplastic, polyurethane elastomer containing thermally labile cross links. It is a further object of this invention to provide the thermoplastic composition which results from this method. Other objects will be apparent from the ensuing description of this invention.

The present invention is based on the discovery that a thermoplastic, polyurethane elastomer with good set characteristics is obtained by curing a prepolymer with a diol compound containing at least one phenolic substituent. Such compounds should be free of other groups reactive with an isocyanate, as for example, thiol carboxyl amino groups.

One class of useful phenolic diols is represented by the Formula I:

OH I

wherein R is lower-alkyl (especially alkyl of 2-4 carbon atoms). Among the compounds represented by Formula I containing both aliphatic and phenolic hydroxy groups are: N,N-di-(2-hydroxyethyl)-p-hydroxyaniline, N,N-di- (2-hydroxypropy1)-p-hydroxyaniline, N,N-di-(2 methyl- 2-hydroxypropyl)-p-hydroxyaniline, N,N-di (2 hydroxyethyl)-meta-hydroxyaniline, N,N-di-(Z hydroxyethyl)-0-hydroxyaniline, and the like,

Thermally labile urethane groups are formed when the phenolic substituent reacts with an isocyanate group. The labile urethane groups thus formed are reversible to the original phenolic and isocyanate groups. The urethane linkages formed from the reaction of the aliphatic hydroxyl and isocyanate groups are stable. Advantage is 3 thus taken of the labile nature of the phenolic urethane group in providing sites for cross-linking and the thermal stability of the aliphatic hydroxyl urethane group.

Polyurethane elastomers of the present invention have the advantage, therefore, of being thermoplastic accord- 4 be used, e.g., a mixture of a phenolic glycol and hydroquinone bis(hydroxyethyl)ether, and the reaction stoichiometry adjusted in a manner as described above. Normally, improved properties are obtained by using a phenolic glycol to supply at least one percent of the ing to the usually accepted definition of the word while 5 total curative requirements and by reacting essentially at the same time, possessing the desirable features of a all of the phenolic groups therein to provide phenolic cross-linked, network structure, viz: a more rapid reurethane cross-links. covery of mechanical properties and improved set char- In order to facilitate the reaction of the phenolic hyacteristics after thermal treatment. droxyl group with the isocyanate, it is generally desirable Any type of polyurethane prepolymer can be cured by that a catalyst be used. Tertiary amines have been found the practice of this invention. Prepolymers can be derived to be efficient catalysts. A preferred catalyst is dimethylfrom polymeric glycols which have a molecular weight dodccylamine. When used to promote the reaction, the of at least 500 and normally less than about 5000, prefcatalyst is used at a concentration of about 0.1 to 1.0%, erably about 600 to 3000. Useful glycols can be either 5 based on the weight of the reactants. polyester glycols or polyalkylene ether glycols. The poly- The reactants, including the catalyst, are thoroughly ester glycols are the condensation products of diols of mixed for a few minutes at a suitable temperature permitabout two to ten carbon atoms and dicarboxylic acids ting a low viscosity and then poured into a suitable conof about two to eight carbon atoms in each alkylene tainer or mold, and cured. The composition may be cured chain. The alkylene linkages in both the polyesters 01 either at a moderately elevated temperature, 1'00-120" C. polyethers may be straight or branch-chained. Typical for about 10 hours, or for a few hours at 100-120" C. glycolic polyesters include those prepared from 1) followed by a longer period of time at some lower temglycols such as ethylene glycols, propylene glycol-1,2, perature, 70-80 C. The time and the temperature of propylene glycol-1,3, butylene glycol-1,4, decamethylene curing are readily determined by conventional techniques glycol and mixtures thereof, and (2) dicarboxylic acids, known to those skilled in the polyurethane art. The resultsuch as succinic, glutaric acid, adipic acid, pimilic acid, ant polymer may be milled on a conventional mill, exsuberic acid, azelaic acid, sebacic acid and mixtures truded or injection molded. If desired, other compoundthereof. ing ingredients, such as antioxidants or fillers, may be Typical glycolic polyethers include polyethylene ether added during the curing step or at some subsequent time, glycol, polytetramethylene ether glycol, poly-1,2-dimethylsuch as during milling. ethylene ether glycol and mixtures thereof. The invention is more fully illustrated by the examples The diisocyanates of use in the preparation of pre which follow. polymers curable by this invention include all the diiso- EXAMPLE 1 cyanates normally used in making polyurethanes. The preferred diisocyanates are the aromatic diisocyanates. pmmophenol 55 grams mole elhylene chloro The present invention will 'be illustrated with respect to hydnn 125 grams moles and sodlum carbonate prepolymers prepared from TODI l 26.5 grams, 0.2? mole, were refluxed for 4.5 hours and phenylene diisocyanate) since this is representative of the reactlon mlxture P mto 300 of a useful diisocyanates. Other suitable aromatic diisocyanates f' l Sodmm carbonate solutlon l F h especially include 2,4-tolylenediisocyanate, 2,6-tolylenedi- 40 clpltate was filtered off and Washed Wlth sodmm blsulfite isocyanate and mixtures thereof, m-phenylene diisocyasohmon and f water- The Product was fecrystaulzed nate, m-xylylene diisocyanate, etc. Non-aromatic diisofrom W t Whlch afforded 60 gramsaof 2:2 '(phydroxy cyanates such as hexamethylenediisocyanate, bis(2-isoy nokthanol, M.P. 140-142 C. Reference: C. cyanatoethyl)carbonate and the like may also be used. Hyvang, CheII 11Ca1 Abstracts 52, 155093, (1958).

The reaction between the polymeric glycol and the Th s example illustrates the preparation of one of the diisocyanate to give the prepolymer is carried out in a curanves useful m the Present mventlon' conventional manner. Stabilizers, solvents, adjuvants, etc. EXAMPLE 2 may be added if desired. The prepolymers thus obtained can be cured by reaction with a phenolic glycol or a fiz g z 21 of ga t i mixture of a phenolic glycol and at least one non-phenolic th 1 i sif 39 ye y 1 a lpa e a glycol, such as hydroquinone bis(hydroxyethyl) ether l'me 1p i em usocyana e) were ad ed (PEHQ), butanedio1-1,4, hexamethylene glycol, etc. grams (98% of t e of PEHQ and (0.2% based on the welght of the reactants) of The amount of curative used m chain-extendrng the gi 1d d 1 Th d prepolymers is normally a stoichiometric amount, i.e., the O ecy 2 5 ingre 1 ere l an amount sulficient to react with all the isocyanate groups. ggif 25 3 i O and t 3 overmghjtb One of the advantages of the compounds of the present b 1 e resu PO ymer was treate as descn e invention rests in the flexibility which they permit in e designing thermoplastic structures for particular require- Molded nt 7 m l Sheets by pressing for 3-5 ments. Thus, a phenolic glycol may be used as the sole minutes d dcurative fo h prepolymer Depending on the degree (B) Molded several times successively under the same of cross-linking desired, from 1 to of the phenolic Commons as m hydroxyl groups may be reacted with the isocyanate The molded sheets A and B were tested for the mechanical groups of the prepolymer in addition to all of the aliproperties using an Instron tester. Results are shown in phatic hydroxyl groups. Similarly, mixed curatives may the accompanying table.

Modulus, p.s.i. Elonga- Die 0 tear Hardness Tensile, tion, Break set, strength Shore A 100% 300% 500% p.s.i. percent percent (p.l.i.)'

*ASTM Method N0. D-624-54.

This example illustrates the properties, especially percent break set, which are obtained with conventional thermoplastic polyurethanes where the only cross-linking is of the allophanate type. It also illustrates the slight loss Modulus, p.s.i. Elonga- Break Die 0 tear Hardness Tensile, tron, Set, strength Shore A 100% 300% 500% p.s.i. percent percent (p.l.i.),

*ASTM Method No. D62454.

of properties on repeated moldings at temperatures.

EXAMPLE 3 To 200 grams (0.131 eq.) of the prepolymer used in Example 2 were added 11.60 grams (90% of the NCO elevated 10 This example illustrates the excellent properties of the polymer even after extensive milling on conventional rubber equipment. Especially indicative of the advantages of the polyfunctional curative of this invention is the low break set data which illustrates the rapid reformation eq.) of alpha, alpha-dihydroxy 4,4 diethoxybenzene' of cross-11PM after mllhng (PEHQ) and 0.86 gram (10% of the NCO eq.) of 2,2'- We clalm: (p-hydroxyphenylimino)diethanol (HPID) an 1. A thermoplastic polyurethane elastomer having regram (0.1% based on the weight of the reactants) of curring llnkages derived from the reaction of an dimethyldodecylamine. The ingredients were mixed and isocyanate-tefminated Polyurethane prepolymer P p cured f 2 hours 1100 C d h overnight 75 C, by reaction of an organic diisocyanate with a hydroxy- The resulting polymer was then treated as in Example 2. terminated polyester, hydroxy-terminated polyether, or Results are shown in the accompanying table. mixture of said polyester and polyether, with a stoichio- Modulus, p.s.i. Elonga- Die 0 tear Hardness Tensile, tion, Break set, strength Shore A 100% 300% 500% p.s.i. percent percent (p.1.i.)

*AS'IM Method No. D-624-54.

This example illustrates the superior break set properties metric amount of (b) a glycol mixture comprising at of the composition of the present invention using the least 1% by weight of a phenolic glycol of the formula: novel curative. The improvement in mechanical properties, as a result of the cross-linked structure, is apparent. Additionally, as shown in B, the composition may be repeatedly molded, without serious effect, like conventional thermoplastics.

EXAMPLE 4 40 011 T 0 290 grams (0.189 eq.) of the prepolymer of Examwherein R is alkyl of 2-4 carbon atoms.

ple 2 were added 16.8 grams (90% of the NCO eq.) of 2. The thermoplastic polyurethane elastomer of claim alpha, alpha'-di'hfdroxy 4,4 diethoxybenzene (PEHQ), 1 wherein R of the glycol formula is ethyl. 125 grams (10% of the NCO eq.) of 2,2-(p-hydroxy- 3. The thermoplastic polyurethane elastomer of claim phenylimino)diethanol (HPID), 1.5 grams (0.5% by 1 wherein R of the glycol formula is propyl. weight) of Antioxidant 2246 and 0.15 gram (0.05% by 4. The thermoplastic polyurethane elastomer of claim weight) of dimethyldodecylamine. The ingredients were 1 wherein the prepolymer (a) is an isocyanate-terminated mixed and cured for 2 days 75 C. The resulting polypolyester of molecular weight below about 5000. mer was preheated in a press 350 F. and then milled 5. The thermoplastic polyurethane elastomer of claim for 5 minutes on a rubber mill 100-110 C. The milled 1 wherein the prepolymer (a) is an isOcyanate-terminated polymer was then molded into sheets as described in Example 2. The cured sheets were tested with the following results:

polyether of molecular weight below about 5000.

6. The thermoplastic polyurethane elastomer of claim Modulus, p.s.i. Elonga- Break Die 0 Tear Hardness Tensile, tion, set, strength Shore A 100% 300% 500% p.s.i. percent percent (p.l.1.)

ASTM Method N0. F-624-54.

This example demonstrates that the cross-linked po1ymer can be successfully milled on conventional rubber processing equipment without excessive breakdown and recover most of the desirable properties. Especially note the improved break set.

EXAMPLE 5 0 1 wherein the glycol mixture b) contains hydroquinone bis (hydroxyethyl) ether.

References Cited UNITED STATES PATENTS 3,044,991 7/ 1962 Muller et al. 260-775 3,063,964 11/1962 Khawam 260 -47 3,282,896 11/1966 Einberg 260-47 WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner US. Cl. X.R. 

